Compound of the distyryl pyridinium salt series and its production



Patented Mar. 12, 19135 term cor/ romp or 'rna nrs'rYaYL PYRrnr niM SALT snares AND rrs PRODUCTION Martin Dabelowand Alfred Philips, Frankfort-- on-the-Vllain,

Germany, assignors to Agfa Ansco Corporation, Binghamton, N. Y., a corpcration of New York No Drawing. Application September 4, 1931, Serial No. 561,304. In Germany September 20,

'15 claims (01. 260-42) Our present invention relates to photographic sensitizers and desensitizersanlda process of preparing them.

We have found that compoundsoi the follow ing formula:

in which R1 and R2 stand for, hydrogen or an alkyl group, R3 stands for hydrogen, an'aliphatic hydrocarbon group, an aromatic hydrocarbon group of the benzene series or an aliphatic-aromatic hydrocarbon group of the benzyl series, R4 stands for an'alky-l' or an aliphatic-aromatic hydrocarbon group of the benzyl series} R5 and Rs stand for a phenyl group, a benzyl group or the group C6H5CH=CH, the benzene nucleus of which may be substituted by the nitro group, a monoalkylamino group or a dialkylaminogroup and X stands for a halogen, the group SO4- alkyl or the group -SO3- aromatic hydrocarbons, the aromatic hydrocarbon being of the henzene series .may be easily prepared by heating two mole of an aromatic aldehyde then'ucle'us in which R1. and R2 stand for hydrogen or an alkyl group, R3 stands for hydrogen, an aliphatic hydrocarbon group, an aromatic hydrocarbon group of the benzene series or an aliphatic-aromatic hydrocarbon group of the benzyl series, R4 stands for an alkyl or an aliphatic aromatic hydrocarbon group of the benzyl series and X stands for a halogen, the group SO4- alkyl or the group -SO3-\-=-'- aromatic hydrocarbons, the aromatic hydrocarbon being of the benzene series. The reaction may be carried out at temperatures between 50 C. and 100 C. The time required for the complete formation of the final product varies between 4-5 hours and several days according to the constitution of the starting materials used and the temperature applied.- When the reaction is compyridine, 2.6 dimethyl-e benzyl-pyridine.

The final products are crystalline compounds, soluble in water and alcohols. They are distin plete, the final products can be easily isolated because they crystallize when the reaction mixture guishedby-their photographically active characfe ter.- The compounds, containing a basic substitu+ ent such as a mono or dialkyl amino group in the nucleiR1 and'Rz may be used as "sensitizers, i; e. they increase the light-sensitiveness of the layers on photographic films, plates and the like to the long-wave rays ofth'e, spectrum. The compounds containing negative substituents in thenucleiRi and R2 for instance the nitro-group, may be used as desensitizers, i. e.--they decreas'e the sensitiveness of photographic layers to the action of light during the development. r v i q a The following examples illustrate the invention, but they are not intendedto limit it thereto: ,1, ,7 1. 1 mol of. 2.6-dimethyl-pyridine ethioclide and 2 mols of l-dimethylaminobenzaldehyde are dissolved in the absence or presence of alcohol and the solution is heated to C.- C. for eight hours or more. ihere may be adde'd 'a small quantity'of piperidine. (The reaction mixture is allowed to cool whereupon-the crystals which have separated are isolated and purified by dissolving and recrystallizing them. The final product shows a melting point of 273 C.

2. 2 mols of 4-diethylaminobenzaldehyde and 1 mol of 1.2.4.6-tetramethylpyridinium-bromide 5 are dissolved in the presence or absence of alcohol andheated to C.- C. for ten hours or more. There may be added a small quantity of piperidine. The crystals which have been isolated from the cold reaction mixture are purified by dissolving-and recrystallizing them.

3. 2 n iols of diniethylamino-cinnamicaldehyde and 1 mol of 2.6-dimethylpyridine-ethiodide are dissolved in the presence or absence of an appropriate solvent and heated to 80 C.- 100 C, for

eight hours or more. There-may be added a small quantity of piperidine. Thecrystalswhich have separated from the cold;reaction mixture are isolated and may be purified by dissolving.

and recrystallizing them; The final"- product shows a melting point of 263 C.

4. 2 mole of 3-nitrobenzaldehyde and 1 mol of 1.2.6-trimethy]pyridiniuni siilforifietliiylaflze of the following formula:

said product being-a crystalline substance showing sensitizing ,properties andbeing soluble in watei'and alcohols. V a Y 3. The command r the following formula:

said product being a crystalline substance showing sensitizing properties and being soluble in water and alcohols.

4: The compound of the following formula:

said product being a crystalline substance showing sensitizing properties and being soluble in water and alcohols. 7

5. The process which comprises heating in the presence of a solvent two mole of an aromaticaldehyde of the benzene series which may be substituted by a mono-alkylamino group,' a dialkylamino group or the nitro group with one mol of a compound of the following formula:

inwhich Ryand R2 stand alkyl group,

R3 stands forhydrogen, an aliphatic hydrocarbon group, an aromatic hydrocarbon group of the for hydrogen or an benzene 's'eries'or an aliphatic-aromatic hydrocarbon "group of, the benzyl'series, Rrstands for an alkyl or an aliphatic-aromatic hydrocarbon group of the benzyl series and X stands for a halogen, the groupSO4-a1ky1 or the group-SOa a romatic hydrocarbom-the aromatic hydrocarbon being 7 of the benzene series.

'6. The process which comprises heating two I,

mols of an aromatic aldehyde of the benzene series which may be substituted by a mono-alkylamino group, a dialkylamin'o group or the nitro group with one mol of a compound of the following formula: V

V a R in which R1 and R2 stand alkyl group,

Rs'stands for'hydrog'eman aliphatichydrocarbon group, an aromatic hydrocarbon group of the benzene series or an' aliphaticearomatic'fhydro carbon'group of the" benzyl series,

R4 stands for an alkyl or an aliphatic-aromatic I hydrocarbon group of the benzyl'series, and X standsfor Cl; Br or I; V

Y on;

for hydrogen or an v 7. The compounds of the following formula:

in which R1 and R2 stand for hydrogenor an alkyl group,

R3 stands for hydrogen, an aliphatic hydrocarbon group, an aromatic hydrocarbon group of the benzene series or an aliphatic-aromatic hydrocarbon group of the benzyl series,

R4 stands for an alkyl or an aliphatic-aromatic hydrocarbon group of the benzyl series,

R5 and Rs stand for a phenyl group, a benzyl group or the group CsH5-CH=CH--, the benzene nucleus of whichmay be substituted by the nitro group, a monoalkylamino group or a dialkylamino group and X stands for Cl, Br or I,

said products being crystalline, photographically active substances, soluble in water and alcohols. 8. The compounds of the following formula:

in which R3 stands for hydrogen, an aliphatic hydrocarbon group, an aromatic hydrocarbon group of the benzene series or an aliphatic-aromatic hydrocarbon group of the benzyl series,

R4 stands for an alkyl or an aliphatic-aromatic hydrocarbon group of the benzyl series.

and X stands for Cl, Br or I,

said products being crystalline substances showing sensitizing properties and being soluble in water and alcohols.

10. The process which comprises heating two mols of an aromatic aldehyde of the benzene series which may be substituted by a mono-alkylamino group, a dialkylamino group or the nitro group with one mol of a compound of the following formula:

the benzene series or an aliphatic-aromatic hydrocarbon group of the benzyl series,

R4 stands for an alkyl or an aliphatic-aromatic hydrocarbon group of the benzyl series and X stands for a halogen, the group-SO4 alkyl or the group -SO3 aromatic hydrocarbon, the

aromatic hydrocarbon being of the benzene se- T165. 7 11. The process which comprises heating two mols of an aromatic aldehyde of the benzene series which may be substituted by a monoalkylamino group, a dialkylamino group or the nitro'group with one mol of a compound of the following formula:

in which R3 stands for hydrogen, an aliphatichydrocarbon group, an aromatic hydrocarbon group of V the benzene series or an aliphatic-aromatic hydrocarbon group of the benzyl series,

R4 stands for an alkyl or an aliphatic-aromatic hydrocarbon group of the benzyl series and X stands for a halogen, the group -SO4 alkyl or the group SO3' aromatic hydrocarbon, the aromatic hydrocarbon being of the benzene series. 3 r 12. The process which comprises heating two mols of benzaldehyde, which may be substitituted by a mono-alkylamino, a dialkylamino group or the nitro group with one mol of a compound of the following formula:

in which R3. stands for hydrogen, an aliphatic hydrocarbon group,-an aromatic hydrocarbon group of the benzene series or an aliphatic-aromatic hydrocarbon group of the benzyl series,

R4 stands for an alkyl or an aliphatic-aromatic hydrocarbon group of the benzyl series and X stands for a halogen, the group --SO4-: alkyl or the group SO3 aromatic; hydrocarbon, the aromatic hydrocarbon being of the benzene series.

13. The compounds of the following formula:

in which R1 and R2 stand for hydrogen or an alkyl group,

R3 stands for hydrogen, an aliphatic hydrocarbon group, an aromatic hydrocarbon group of the benzene series or an aliphatic-aromatic hydrocarbon group of the benzyl series,

R4 stands for an alkyl or an aliphatic-aromatic hydrocarbon group of the benzyl series,

R5 and Re stand for a phenyl group, a benzyl group or the group CsH5CI-I=CH-, the henzene nucleus of which may be substituted by the nitro group, a monoalkylamino group or a dialkylamino group and X stands for a halogen, the group SO4-alkyl or the group SO3-aromatic hydrocarbon, the aromatic hydrocarbon being of the benzene series, I

said products being crystalline, photographically active substances, soluble in water and alcohols. 14. The compounds of the following formula:

n which R3 stands 'forhydrogen, an aliphatic hydrocarbon group, an aromatic hydrocarbon group or the benzene series or an aliphatic-aromatichydrocarbon group of the benzyl series,

R4 stands for an alkyl or: an aliphatic-aromatic! hydrocarbon group of the benzyl series, R5 and Rs stand for a phenyl group, a benzyl group or the group CsH5CH=CH-, the ben 'zene nucleus of which may be substituted by the nitro group, a monoalkylamino grouper a dialkylarnino group and the group SO3 -aromatic hydrocarbonfthe aromatic hydrocarbon being of the benzene series,

said products being crystalline, photographically.

active substances, soluble vin' water and alcohols. r 15 The compounds of the followingformula:

in which R3 stands for hydrogen, an aliphatic hydrocarbon group, an aromatic hydrocarbon group of the benzene series or an aliphatic-aromatic hydrocarbon group of the benzyl series,

R4 stands for an alkyl or: an aliphatic-aromatic hydrocarbon group of thebenzyl series and X stands for a halogen, the group -SO4- alkyl or the group SOs-aromatic hydrocarbon, the aromatic hydrocarbon being of thebenzene' series,

V 10 X stands for a halogen, the group ,-SO4'-al k y1'orsaid'products being crystalline substances showing sensitizing properties Water and alcohols.

ALFRED PHILIl?S and being soluble in l L MARTIN DABELOWI. I 

